Crystal-to-glass transformation is a powerful approach to modulating the chemical and physical properties of crystals. Here we demonstrate that the glass transformation of cobalt hexacyanoferrate crystals, one of the Prussian blue analogues, increased the concentration of open metal sites and altered the electronic state while maintaining coordination geometries and short-range ordering in the structure. The compositional and structural changes were characterized by X-ray absorption fine structure, energy dispersive X-ray spectroscopy, and X-ray total scattering. The changes contribute to the flat band potential of the glass becoming closer to the redox potential of CO₂ reduction. The valence band energy of the glass also shifts, resulting in lower band gap energy. Both the increased open metal sites and the optimal electronic structure upon vitrification enhance photocatalytic activity toward CO₂-to-CO conversions (9.9 μmol h^–1 CO production) and selectivity (72.4%) in comparison with the crystalline counterpart (3.9 μmol h^–1 and 42.8%).

中文翻译：

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用于光诱导二氧化碳转化的普鲁士蓝模拟玻璃


晶体到玻璃的转变是调节晶体化学和物理性质的有效方法。在这里，我们证明了六氰基铁酸钴晶体（普鲁士蓝类似物之一）的玻璃转变增加了开放金属位点的浓度并改变了电子态，同时保持了结构中的配位几何形状和短程有序。通过X射线吸收精细结构、能量色散X射线光谱和X射线全散射来表征成分和结构变化。这些变化有助于玻璃的平带电势变得更接近CO ₂还原的氧化还原电势。玻璃的价带能量也会发生变化，导致带隙能量降低。与晶体对应物 (3.9 μmol h ^–1)相比，增加的开放金属位点和玻璃化时的最佳电子结构都增强了 CO ₂转化为 CO 的光催化活性（9.9 μmol h ^–1 CO 产量）和选择性 (72.4%)。 ¹和 42.8%）。